CN112742482A - Catalyst for catalytic hydrogenation, preparation method and application thereof - Google Patents
Catalyst for catalytic hydrogenation, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of catalyst material preparation, and discloses a catalyst for catalytic hydrogenation, and a preparation method and application thereof. The catalyst comprises a metal organic framework compound and two metals doped on the metal organic framework compound; the two metals are copper and cobalt. The catalyst has high catalytic transfer hydrogenation activity under mild conditions, and shows high conversion rate and high selectivity. When the catalyst is applied to catalyzing 5-hydroxymethylfurfural to prepare 2, 5-dimethylolfuran, the conversion rate of 5-hydroxymethylfurfural is more than 97 percent and reaches as high as 99.5 percent; the selectivity of 2, 5-dihydroxymethylfuran is greater than 95% and as high as 97.7%. The catalyst also has good stability and recycling property. The catalyst is synthesized by a solvothermal reaction and a one-step method, and has the advantages of simple preparation method, simple and convenient operation and high preparation efficiency.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and particularly relates to a catalyst for catalytic hydrogenation, and a preparation method and application thereof.
Background
Due to the ever-decreasing availability of fossil resources, it has become important to find alternative resources for the production of fuels and chemicals. Biomass resources are widely available and abundant, and can be recycled through photosynthesis, so that zero carbon emission can be realized, and the biomass resources are concerned by more and more researchers. 5-Hydroxymethylfurfural (HMF) can be prepared by dehydrating glucose, fructose and the like, is easy to obtain, can produce a large amount of derivatives with high added value by the preparation method, and has important platform property, so the preparation method is concerned by researchers. The products of the 5-hydroxymethylfurfural reaction include not only 2, 5-furandimethanol (DHMF) which can be applied to the synthesis of ethers, ketones, resins and the like, but also high-quality liquid fuels including 2, 5-Dimethylfuran (DMF), ethyl levulinate, 5-ethoxymethylfurfural and long-chain alkanes, and other various high value-added chemicals such as 2, 5-furandicarbaldehyde and levulinic acid.
In previous researches, a noble metal catalyst and hydrogen are mostly adopted as a catalytic system for catalyzing hydrogenation reaction to catalyze 5-Hydroxymethylfurfural (HMF) to prepare 2, 5-furandimethanol (DHMF), so that excellent activity results are obtained; however, the use of noble metal catalysts is costly, and hydrogen (as a hydrogen source) is derived from non-renewable fossil energy sources, and is inconvenient to transport and store, and has potential safety hazards during use. Or the material containing the metal organic framework compound is adopted as the catalyst, but the preparation method of the existing catalyst containing the metal organic framework compound is complex, and the process is not easy to control; and a high catalytic temperature (at least 120 ℃) is needed to realize good catalytic activity.
Therefore, it is highly desirable to provide a catalyst for catalytic hydrogenation, which can exhibit high catalytic activity under mild conditions and has a simple preparation method.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a catalyst for catalytic hydrogenation, which can show higher catalytic activity under mild conditions (lower than 120 ℃) and has a simple preparation method.
The invention provides a catalyst for catalytic hydrogenation, which comprises metal organic framework compounds (MOFs) and two metals doped on the metal organic framework compounds; the two metals are copper and cobalt.
Preferably, the doping amount of the copper is 0.01-0.15%; the doping amount of the cobalt is 0.05-0.4%; further preferably, the doping amount of the copper is 0.01% -0.1%; the doping amount of the cobalt is 0.05-0.3%.
Preferably, the metal organic framework compound is UIO-66 or UIO-66-NH2、UIO-66-NO2UIO-66-OH or UIO-66-SO3H.
Preferably, the particle size of the catalyst is 150-500 nm; further preferably, the particle size of the catalyst is 200-400 nm.
The invention also provides a preparation method of the catalyst for catalytic hydrogenation, which comprises the following steps:
(1) respectively dissolving zirconium salt, a ligand and two metal salts in a solvent to obtain a zirconium salt solution, a ligand solution and a metal salt solution, then mixing the zirconium salt solution, the ligand solution and the metal salt solution, and adding a regulator to obtain a mixed solution;
(2) and (2) carrying out solvent thermal reaction on the mixed solution prepared in the step (1), and filtering to obtain filter residue, namely the catalyst.
Preferably, in the step (1), the ligand is a compound containing a terephthalic acid structure; further preferably, the ligand is selected from at least one of terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-hydroxyterephthalic acid or 2-sulfoterephthalic acid monosodium salt.
Preferably, in step (1), the metal salt is a copper salt and a cobalt salt.
Preferably, in step (1), the solvent is selected from at least one of methanol, ethanol, or N, N-dimethylformamide.
Preferably, in the step (1), the concentration of the zirconium salt in the zirconium salt solution is 0.08-0.12mol/L, and the concentration of the ligand in the ligand solution is 0.08-0.16 mol/L.
Preferably, in the mixed solution of step (1), the molar ratio of the zirconium salt to the ligand is (0.5-2): (0.5-3); further preferably, the molar ratio of the zirconium salt to the ligand is (1-1.5): (1-2); more preferably, the molar ratio of the zirconium salt to the ligand is 1: 1.
preferably, in the step (1), the total concentration of the metal salts in the metal salt solution is 0.015 to 0.20 mol/L; further preferably, the total concentration of the metal salts in the metal salt solution is 0.016-0.16 mol/L.
Preferably, in step (1), the molar ratio of the zirconium salt to the metal salt is (0.5-2): (0.5-3); further preferably, the molar ratio of the zirconium salt to the metal salt is (1-1.5): (1-2).
Preferably, in the step (1), the mixing of the zirconium salt solution, the ligand solution and the metal salt solution is performed by: adding a ligand solution into the zirconium salt solution to obtain a mixed solution, and adding the metal salt solution into the mixed solution. The preparation solution is added respectively, which is beneficial to the formation of the final catalyst, and the prepared catalyst has good appearance. If the zirconium salt, ligand and metal salt are added directly to the solvent and mixed, the morphology of the catalyst will be affected.
Further preferably, in the step (1), the mixing of the zirconium salt solution, the ligand solution and the metal salt solution is performed by: adding a ligand solution into the zirconium salt solution at the speed of 3-5ml/min to obtain a mixed solution, and adding the metal salt solution into the mixed solution at the speed of 3-5 ml/min.
Preferably, in step (1), the regulator is at least one of formic acid, acetic acid or benzoic acid.
Preferably, in the step (2), the mixed solution is subjected to ultrasonic treatment before the solvothermal reaction, the power of the ultrasonic treatment is 200-400W, and the time of the ultrasonic treatment is 10-30 min.
Preferably, in the step (2), the solvent thermal reaction is carried out by placing the mixed solution in a hydrothermal kettle and reacting at 110-150 ℃ for 12-48 h.
Specifically, the preparation method of the catalyst for catalytic hydrogenation comprises the following steps:
respectively dissolving zirconium salt, a ligand and two metal salts in a solvent to obtain a zirconium salt solution, a ligand solution and a metal salt solution, then adding the ligand solution into the zirconium salt solution at the speed of 3-5ml/min, and then stirring at the speed of 300-600rpm for 20-60min to obtain a mixed solution; adding a metal salt solution into the mixed solution at the speed of 3-5ml/min, stirring at the speed of 300-600rpm for 20-60min, adding a regulator into the mixed solution to obtain a mixed solution, performing ultrasonic treatment, performing solvothermal reaction on the mixed solution to obtain a reaction solution, filtering the reaction solution, washing a precipitate with a solvent, and performing vacuum drying on the precipitate at the temperature of 60-80 ℃ for 10-24 hours to obtain the catalyst.
The invention also provides the application of the catalyst for catalytic hydrogenation in catalytic transfer hydrogenation reaction.
The catalyst is applied to catalyzing the aldehyde group-containing compound transfer hydrogenation reaction.
The catalyst is applied to the preparation of 2, 5-dihydroxymethyl furan.
The catalyst is applied to the preparation of 2, 5-dihydroxymethylfuran by catalyzing 5-hydroxymethylfurfural.
Preferably, the method for preparing 2, 5-dihydroxymethylfuran by catalyzing 5-hydroxymethylfurfural by the catalyst is as follows:
mixing 5-hydroxymethylfurfural, the catalyst, benzene and a solvent, reacting under the condition of inert gas pressurization, cooling, filtering, and removing filtrate to obtain the 2, 5-dihydroxymethylfuran.
Preferably, the mass ratio of the 5-hydroxymethylfurfural to the catalyst is 1 (0.1-1).
Preferably, the solvent is at least one of methanol, ethanol, isopropanol, n-butanol or 2-butanol. Further preferably, the solvent is 2-butanol.
Preferably, the inert gas is nitrogen or a noble gas.
Preferably, the pressure of the pressurization is 0 to 3 MPa; further preferably, the pressure of the pressurization is 1.5 to 3 MPa.
Preferably, the reaction temperature is 80-115 ℃, and the reaction time is 1-8 h; further preferably, the reaction temperature is 90-110 ℃, and the reaction time is 1-8 h.
Due to the alcoholic hydroxyl group, aldehyde group and furan ring contained in HMF (5-hydroxymethylfurfural), the key to obtaining DHMF (2, 5-dimethylolfuran) is to hydrogenate only the aldehyde group and not the other functional groups. Therefore, the selection of a proper catalytic system has important significance for improving the activity of converting HMF into DHMF. The invention selects metal organic framework compound, and utilizes the high surface area and porosity of the metal organic framework compound to dope bimetal to prepare the catalyst. The inventors have surprisingly found that bimetallic (copper and cobalt) doped catalysts can exhibit high conversion and selectivity at lower temperatures and shorter reaction times than catalysts made from MOFs doped with a single metal. After the bimetal (copper and cobalt) is doped, the metal organic framework compound still can keep an octahedral framework, has a stable structure and stable catalytic performance, still has higher conversion rate and selectivity after being used for multiple times of circular catalysis, and the performances are incomparable to catalysts prepared by doping MOFs materials with single metal and incomparable to catalysts prepared by doping other bimetal.
Meanwhile, the bimetallic doped catalyst is synthesized by a one-step method through a solvothermal reaction, and the preparation method is simple, simple and convenient to operate and high in preparation efficiency.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst is prepared by selecting a metal organic framework compound and doping copper and cobalt double metals, has high catalytic transfer hydrogenation activity under mild conditions (the catalytic temperature is lower than 120 ℃), and shows high conversion rate and high selectivity. When the catalyst is applied to catalyzing 5-hydroxymethylfurfural to prepare 2, 5-dimethylolfuran, the conversion rate of HMF (5-hydroxymethylfurfural) is more than 97 percent and reaches as high as 99.5 percent; the selectivity of DHMF (2, 5-dimethylolfuran) is greater than 95% and as high as 97.7%.
(2) The catalyst provided by the invention has good stability and reusability, and still has higher conversion rate and selectivity after being recycled for many times.
(3) The invention synthesizes the bimetallic doped catalyst by a one-step method through solvothermal reaction, and has the advantages of simple preparation method, simple and convenient operation and high preparation efficiency.
Drawings
FIG. 1 is an SEM photograph of the catalyst prepared in example 3;
FIG. 2 is an X-ray diffraction pattern of the catalyst prepared in example 3;
FIG. 3 is a TEM image of the catalyst obtained in example 3;
fig. 4 is a bar graph of HMF conversion and DHMF selectivity for the catalyst prepared in example 3 in 5 catalytic HMF transfer hydrogenations cycles.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A catalyst for catalytic hydrogenation contains metal organic skeleton compound UIO-66-NH2And doping with a metal-organic framework compound UIO-66-NH2Cobalt and copper.
The preparation method of the catalyst comprises the following steps:
respectively dissolving 0.373g of zirconium chloride and 0.435g of 2-aminoterephthalic acid in 20mL of N, N-dimethylformamide, dissolving 0.1523g of cobalt chloride hexahydrate and 0.1637g of copper chloride dihydrate in 10mL of N, N-dimethylformamide, stirring at 500rpm for 30 minutes to obtain a mixed solution of the zirconium chloride solution, the 2-aminoterephthalic acid solution and the cobalt chloride hexahydrate and the copper chloride dihydrate, dropwise adding the 2-aminoterephthalic acid solution into the zirconium chloride solution at the speed of 4mL/min, uniformly mixing and stirring, dropwise adding the mixed solution of the cobalt chloride hexahydrate and the copper chloride dihydrate at the speed of 4mL/min into the solution, uniformly mixing and stirring, adding 10mL of glacial acetic acid solution into the mixed solution, stirring for 30 minutes, performing ultrasonic treatment at the power of 300W for 20 minutes to obtain a mixed solution, transferring the mixed solution into a stainless steel sealed polytetrafluoroethylene reaction kettle, and reacting for 48 hours at 120 ℃, after the reaction kettle is cooled, centrifugally separating reaction liquid to obtain a solid, washing the solid for three times by using N, N-dimethylformamide and ethanol respectively, and taking a precipitate to perform vacuum drying for 24 hours at 60 ℃ to obtain the catalyst 1.
The preparation method of 2, 5-dihydroxymethylfuran by catalyzing 5-hydroxymethylfurfural with a catalyst 1 comprises the following steps:
to a 100ml autoclave were added reactants 0.2g HMF, 0.1g catalyst 1, 0.05g toluene and 30ml 2-butanol, purged with nitrogen to remove dissolved O2Or air, then 2MPa nitrogen is introduced, the reaction is carried out for 4 hours at 100 ℃ and the mechanical stirring speed of 600rpm, after the reaction is finished, the temperature is rapidly cooled to room temperature, the reaction liquid is filtered to obtain a DHMF product, and the activity result is obtained after gas chromatography analysis.
Example 2
A catalyst for catalytic hydrogenation contains metal organic skeleton compound UIO-66-NH2And doping with a metal-organic framework compound UIO-66-NH2Cobalt and copper.
The preparation method of the catalyst comprises the following steps:
respectively dissolving 0.373g of zirconium chloride and 0.29g of 2-aminoterephthalic acid in 20mL of N, N-dimethylformamide, dissolving 0.114g of cobalt chloride hexahydrate and 0.191g of copper chloride dihydrate in 10mL of N, N-dimethylformamide, stirring at 600rpm for 40 minutes to obtain a mixed solution of the zirconium chloride solution, the 2-aminoterephthalic acid solution and the cobalt chloride hexahydrate and the copper chloride dihydrate, dropwise adding the 2-aminoterephthalic acid solution into the zirconium chloride solution at the speed of 3mL/min, uniformly mixing and stirring, dropwise adding the mixed solution of the cobalt chloride hexahydrate and the copper chloride dihydrate at the speed of 3mL/min into the solution, uniformly mixing and stirring, adding 10mL of glacial acetic acid solution into the mixed solution, stirring for 40 minutes, performing ultrasonic treatment at the power of 300W for 20 minutes to obtain a mixed solution, transferring the mixed solution into a stainless steel sealed polytetrafluoroethylene reaction kettle, and reacting at 120 ℃ for 24 hours, after the reaction kettle is cooled, centrifugally separating reaction liquid to obtain a solid, washing the solid with N, N-dimethylformamide and ethanol for three times respectively, and taking a precipitate to be dried under vacuum at 70 ℃ for 24 hours to obtain the catalyst 2.
The method for preparing 2, 5-dihydroxymethylfuran by catalyzing 5-hydroxymethylfurfural with a catalyst 2 comprises the following steps:
to a 100ml autoclave were added reactants 0.2g HMF, 0.1g catalyst 2, 0.05g toluene and 30ml 2-butanol, purged with nitrogen to remove dissolved O2Or air, then 2MPa nitrogen is introduced, the reaction is carried out for 5 hours at 100 ℃ and the mechanical stirring speed of 500rpm, after the reaction is finished, the temperature is rapidly cooled to room temperature, the reaction liquid is filtered to obtain a DHMF product, and the activity result is obtained after gas chromatography analysis.
Example 3
A catalyst for catalytic hydrogenation contains metal organic skeleton compound UIO-66-NH2And doping with a metal-organic framework compound UIO-66-NH2Cobalt and copper.
The preparation method of the catalyst comprises the following steps:
respectively dissolving 0.373g of zirconium chloride and 0.29g of 2-aminoterephthalic acid in 20mL of N, N-dimethylformamide, dissolving 0.076g of cobalt chloride hexahydrate and 0.218g of copper chloride dihydrate in 10mL of N, N-dimethylformamide, stirring at 400rpm for 30 minutes to obtain a mixed solution of the zirconium chloride solution, the 2-aminoterephthalic acid solution, the cobalt chloride hexahydrate and the copper chloride dihydrate, dropwise adding the 2-aminoterephthalic acid solution into the zirconium chloride solution at the speed of 4mL/min, uniformly mixing and stirring, dropwise adding the mixed solution of the cobalt chloride hexahydrate and the copper chloride dihydrate at the speed of 4mL/min into the solution, uniformly mixing and stirring, adding 10mL of glacial acetic acid solution into the mixed solution, stirring for 30 minutes, performing ultrasonic treatment at the power of 400W for 15 minutes to obtain a mixed solution, transferring the mixed solution into a stainless steel sealed polytetrafluoroethylene reaction kettle, and reacting for 36 hours at 120 ℃, after the reaction kettle is cooled, centrifugally separating reaction liquid to obtain a solid, washing the solid for three times by using N, N-dimethylformamide and methanol respectively, and taking a precipitate to carry out vacuum drying for 24 hours at 60 ℃ to obtain the catalyst 3.
The method for preparing 2, 5-dihydroxymethylfuran by catalyzing 5-hydroxymethylfurfural with a catalyst 3 comprises the following steps:
to a 100ml autoclave were added reactants 0.2g HMF, 0.1g catalyst 3, 0.05g toluene and 30ml 2-butanol, purged with nitrogen to remove dissolved O2Or air, then 2MPa nitrogen is introduced, the reaction is carried out for 4 hours at 100 ℃ and the mechanical stirring speed of 400rpm, after the reaction is finished, the temperature is rapidly cooled to room temperature, the reaction liquid is filtered to obtain a DHMF product, and the activity result is obtained after gas chromatography analysis.
FIG. 1 is an SEM image of catalyst 3 obtained in example 3, from which it can be seen that catalyst 3 has an octahedral structure, but has a non-uniform particle size, indicating successful metal doping. FIG. 2 is an X-ray diffraction pattern of the catalyst obtained in example 3, and it can be seen from FIG. 2 that catalyst 3 still has all the characteristic peaks of UIO-66-NH2 without changing the original crystal structure of MOFs. FIG. 3 is a TEM image of catalyst 3 obtained in example 3. from FIG. 3, it can be seen that the catalyst still has an octahedral structure, and the particle size of the catalyst is 200-400 nm. Fig. 4 is a bar graph of HMF conversion and DHMF selectivity for catalyst 3 prepared in example 3 in 5 catalytic HMF transfer hydrogenations with the ordinate being HMF conversion and DHMF selectivity and the abscissa being the cycle period. The black bars represent conversion of HMF and the gray bars represent selectivity of DHMF. As can be seen from the figure, the catalyst still has higher conversion rate and selectivity after being used for multiple times of circulation catalysis.
Comparative example 1 (the difference between comparative example 1 and example 3 is that the metal-organic framework compound is doped with cobalt only)
A catalyst for catalytic hydrogenation contains metal organic skeleton compound UIO-66-NH2And doping with a metal-organic framework compound UIO-66-NH2And (3) cobalt (II).
The preparation method of the catalyst comprises the following steps:
respectively dissolving 0.373g of zirconium chloride and 0.29g of 2-aminoterephthalic acid in 20mL of N, N-dimethylformamide, dissolving 0.381g of cobalt chloride hexahydrate in 10mL of N, N-dimethylformamide, stirring at 400rpm for 30 minutes to obtain a zirconium chloride solution, a 2-aminoterephthalic acid solution and a cobalt chloride hexahydrate solution, dropwise adding the 2-aminoterephthalic acid solution into the zirconium chloride solution at a speed of 4mL/min, uniformly mixing and stirring, dropwise adding the cobalt chloride hexahydrate solution into the solution at a speed of 4mL/min, uniformly mixing and stirring, adding 10mL of glacial acetic acid solution, stirring for 30 minutes, performing ultrasonic treatment at a power of 400W for 15 minutes to obtain a mixed solution, transferring the mixed solution into a stainless steel sealed polytetrafluoroethylene reaction kettle, reacting at 120 ℃ for 36 hours, after the reaction kettle is cooled, the reaction liquid is centrifugally separated to obtain a solid, the solid is respectively washed for three times by N, N-dimethylformamide and methanol, and the precipitate is taken and dried for 24 hours in vacuum at the temperature of 60 ℃, thus obtaining the catalyst 4.
The method for preparing 2, 5-dihydroxymethylfuran by catalyzing 5-hydroxymethylfurfural with a catalyst 4 comprises the following steps:
to a 100ml autoclave were added reactants 0.2g HMF, 0.1g catalyst 4, 0.05g toluene and 30ml 2-butanol, purged with nitrogen to remove dissolved O2Or air, then 2MPa nitrogen is introduced, the reaction is carried out for 4 hours at 100 ℃ and the mechanical stirring speed of 400rpm, after the reaction is finished, the temperature is rapidly cooled to room temperature, the reaction liquid is filtered to obtain a DHMF product, and the activity result is obtained after gas chromatography analysis.
Comparative example 2 (comparative example 2 differs from example 3 in that the metal-organic framework compound is doped with copper only)
A catalyst for catalytic hydrogenation contains metal organic skeleton compound UIO-66-NH2And doping with a metal-organic framework compound UIO-66-NH2Copper (c) above.
The preparation method of the catalyst comprises the following steps:
respectively dissolving 0.373g of zirconium chloride and 0.29g of 2-amino terephthalic acid in 20mL of N, N-dimethylformamide, dissolving 0.2728g of copper chloride dihydrate in 10mL of N, N-dimethylformamide, stirring at 400rpm for 30 minutes to obtain a zirconium chloride solution, a 2-amino terephthalic acid solution and a copper chloride dihydrate solution, dropwise adding the 2-amino terephthalic acid solution into the zirconium chloride solution at a speed of 4mL/min, uniformly mixing and stirring, dropwise adding the copper chloride dihydrate solution into the above solution at a speed of 4mL/min, uniformly mixing and stirring, adding 10mL of glacial acetic acid solution, stirring for 30 minutes, performing ultrasonic treatment at a power of 400W for 15 minutes to obtain a mixed solution, transferring the mixed solution into a stainless steel sealed polytetrafluoroethylene reaction kettle, and reacting at 120 ℃ for 36 hours, after the reaction kettle is cooled, the reaction liquid is centrifugally separated to obtain a solid, the solid is respectively washed for three times by N, N-dimethylformamide and methanol, and the precipitate is taken and dried for 24 hours in vacuum at the temperature of 60 ℃, thus obtaining the catalyst 5.
The preparation method of 2, 5-dihydroxymethylfuran by catalyzing 5-hydroxymethylfurfural with a catalyst 5 comprises the following steps:
to a 100ml autoclave were added reactants 0.2g HMF, 0.1g catalyst 5, 0.05g toluene and 30ml 2-butanol, purged with nitrogen to remove dissolved O2Or air, then 2MPa nitrogen is introduced, the reaction is carried out for 4 hours at 100 ℃ and the mechanical stirring speed of 400rpm, after the reaction is finished, the temperature is rapidly cooled to room temperature, the reaction liquid is filtered to obtain a DHMF product, and the activity result is obtained after gas chromatography analysis.
Comparative example 3 (the difference between comparative example 3 and example 3 is that cobalt and nickel are doped in the metal-organic framework compound)
A catalyst for catalytic hydrogenation contains metal organic skeleton compound UIO-66-NH2And doping with a metal-organic framework compound UIO-66-NH2Cobalt and nickel.
The preparation method of the catalyst comprises the following steps:
respectively dissolving 0.373g of zirconium chloride and 0.29g of 2-aminoterephthalic acid in 20mL of N, N-dimethylformamide, dissolving 0.1904g of cobalt chloride hexahydrate and 0.1903g of nickel chloride hexahydrate in 10mL of N, N-dimethylformamide, stirring at 400rpm for 60 minutes to obtain a mixed solution of the zirconium chloride solution, the 2-aminoterephthalic acid solution, the cobalt chloride hexahydrate and the nickel chloride hexahydrate, dropwise adding the 2-aminoterephthalic acid solution into the zirconium chloride solution at the speed of 5mL/min, uniformly mixing and stirring, dropwise adding the mixed solution of the cobalt chloride hexahydrate and the nickel chloride hexahydrate into the solution at the speed of 5mL/min, uniformly mixing and stirring, adding 10mL of glacial acetic acid solution into the mixed solution, stirring for 60 minutes, performing ultrasonic treatment at the power of 200W for 30 minutes to obtain a mixed solution, transferring the mixed solution into a stainless steel sealed polytetrafluoroethylene reaction kettle, and reacting at 120 ℃ for 24 hours, after the reaction kettle is cooled, centrifugally separating reaction liquid to obtain a solid, washing the solid with N, N-dimethylformamide and methanol for three times respectively, and taking a precipitate to be dried in vacuum at 80 ℃ for 12 hours to obtain the catalyst 6.
The method for preparing 2, 5-dihydroxymethylfuran by catalyzing 5-hydroxymethylfurfural with a catalyst 6 comprises the following steps:
to a 100ml autoclave were added the reactants 0.2g HMF, 0.1g catalyst 6, 0.05g toluene and 30ml 2-butanol, purged with nitrogen to remove dissolved O2Or air, then 2MPa nitrogen is introduced, the reaction is carried out for 4 hours at 100 ℃ and the mechanical stirring speed of 400rpm, after the reaction is finished, the temperature is rapidly cooled to room temperature, the reaction liquid is filtered to obtain a DHMF product, and the activity result is obtained after gas chromatography analysis.
Product effectiveness testing
The activity of the product obtained after the catalytic reaction of the catalysts 1-6 is analyzed by gas chromatography, the conversion rate of HMF and the selectivity of DHMF are calculated, and the specific activity data are shown in Table 1.
TABLE 1 reactivity data of catalysts prepared in examples and comparative examples
| HMF conversion | DHMF selectivity | |
| Example 1 | 97.7％ | 95％ |
| Example 2 | 97.9％ | 95.5％ |
| Example 3 | 99.5％ | 97.7％ |
| Comparative example 1 | 95.6％ | 77.9％ |
| Comparative example 2 | 87.5％ | 66.5％ |
| Comparative example 3 | 84.8％ | 60.8％ |
As can be seen from Table 1, the catalysts obtained in examples 1-3 all had higher HMF conversion and DHMF selectivity. The catalysts prepared in comparative examples 1-3 had significantly lower HMF conversion and DHMF selectivity than those of examples 1-3. In comparative example 1, on the basis of example 3, the DHMF selectivity is obviously reduced without doping copper; comparative example 2 is based on example 3 with undoped cobalt, reduced HMF conversion and reduced DHMF selectivity. Comparative example 3 the HMF conversion and DHMF selectivity were reduced by replacing copper with nickel on the basis of example 3. Therefore, the activity of the catalyst can be influenced by adding the metal, and the reaction activity can be greatly improved by doping the copper and cobalt double metals. The above examples all have high activity and relatively mild reaction conditions. The catalyst is simple to prepare, and has good stability and recycling property.
Claims (10)
1. A catalyst comprising a metal organic framework compound and two metals doped on the metal organic framework compound; the two metals are copper and cobalt.
2. The catalyst of claim 1, wherein the doping amount of copper is 0.01% -0.15%; the doping amount of the cobalt is 0.05-0.4%.
3. The catalyst of claim 1, wherein the metal organic framework compound is UIO-66, UIO-66-NH2、UIO-66-NO2UIO-66-OH or UIO-66-SO3H.
4. The catalyst as set forth in claim 1, wherein the particle size of the catalyst is 200-400 nm.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, characterized by comprising the steps of:
(1) respectively dissolving zirconium salt, a ligand and two metal salts in a solvent to obtain a zirconium salt solution, a ligand solution and a metal salt solution, then mixing the zirconium salt solution, the ligand solution and the metal salt solution, and adding a regulator to obtain a mixed solution;
(2) and (2) carrying out solvent thermal reaction on the mixed solution prepared in the step (1), and filtering to obtain filter residue, namely the catalyst.
6. The production method according to claim 5, wherein in the step (1), the ligand is a compound containing a terephthalic acid structure; preferably, the ligand is selected from at least one of terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-hydroxyterephthalic acid or 2-sulfoterephthalic acid monosodium salt.
7. The method according to claim 5, wherein the concentration of the zirconium salt in the solution of the zirconium salt is 0.08 to 0.12 mol/L; the concentration of the ligand in the ligand solution is 0.08-0.16 mol/L; the total concentration of the metal salt in the metal salt solution is 0.015-0.20 mol/L.
8. The method as claimed in claim 5, wherein the solvent thermal reaction is carried out by placing the mixed solution in a hydrothermal kettle and reacting at 110-150 ℃ for 12-48 h.
9. Use of a catalyst according to any one of claims 1 to 4 in catalytic transfer hydrogenation reactions.
10. Use of a catalyst according to any one of claims 1 to 4 in the preparation of 2, 5-dimethylolfuran.
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